Organometallic compounds

ABSTRACT

Organometallic compounds and compositions comprising a metal, an amido carboxyl moiety bonded to the metal, an active moiety bonded to the metal, and at least one modifier moiety sufficient to satisfy the valency of the metal. These compounds and compositions are capable of combining the substantivity of the amido carboxyl metal system, functional efficacy of an active moiety, and film-forming properties in a single compound or composition.

FIELD OF THE INVENTION

This invention relates to organometallic compounds, to compositions ofsuch compounds and to formulations incorporating such compounds andcompositions.

BACKGROUND OF THE INVENTION

Complex organometallic soaps are known in the art. Metallic soaps havelong been used in a variety of applications, including such uses asgelling agents for hydrocarbons, as drying agents for paints andvarnishes, as catalysts, as surface active agents and the like. Morespecifically, organometallic compounds of aluminum, titanium, tin andzirconium are known.

Complex aluminum soaps comprising variously substituted carboxylic acidanions have long been used as gelling agents in grease compositions.Illustrative patents disclosing such soaps for grease applications areU.S. Pat. Nos. 2,768,138, 3,591,505, and 4,280,917.

Organoaluminum compounds have also been used in air drying compositionssuch as paints and varnishes and the like. For example, U.S. Pat. No.4,090,886 discloses an air drying media which contains an organoaluminumcompound. The media is stated to be stable for storage, although itincludes an aluminum compound at a ratio of aluminum complex to reactivepaint media which would otherwise be unstable and which would beexpected to gel prior to application. The organoaluminum compounddisclosed in U.S. Pat. No. 4,090,886 comprises certain labilemonofunctional reactants which it is stated will react preferentially toimpede the complex association which would otherwise occur when aluminumcompounds are added to drying oils or paint media which contain reactivegroups, such as, for example, hydroxyl and carboxyl radicals. Theorganoaluminum compounds disclosed in U.S. Pat. No. 4,090,886 mayinclude moieties from monocarboxylic acids, half-esters of dicarboxylicacids and aminocarboxylic acids.

Organotin compounds, and more particularly tin carboxylates, are wellknown as catalysts for the reaction between an organic isocyanate andorganic compounds having an active hydrogen group in the preparation ofpolyurethane. For example, U.S. Pat. No. 4,360,670 discloses amino andamido dialkyl tin dicarboxylates useful as high activity polyurethanecatalysts.

Organotitanium compounds are also known. Such compounds may be preparedfrom tetraalkyl ortho titanates by reaction with organic acids. Thus,organo-titanates comprising carboxylates are disclosed in U.S. Pat No.4,098,758 and alkoxy titanate salts useful as surface active agents aredisclosed in U.S. Pat. No. 4,122,062.

U.S. Pat. No. 4,098,758 discloses an organo-titanate havingnon-hydrolyzable carboxylate groups preferably formed from organic acidshaving 6 to 24 carbon atoms. It is stated that the carboxylate group maybe substituted with amino and carboxyl groups as well as othersubstituents and may contain intermediate hetero atoms, includingnitrogen, among others.

In U.S. Pat. No. 4,122,062 the alkoxy titanate salts disclosed includeone moiety selected from the group consisting of thioaroxy, sulfonyl,sulfinyl, diester pyrophosphate, diester phosphate or substitutedderivatives thereof, and another moiety which is an acyloxy or aryloxy.

Polymer complex carriers for an active ingredient are disclosed in U.S.Pat. No. 3,966,902. The polymer comprises a monomer having hydrophilicfunctional groups and contains aluminum, zinc, or zirconium bound incomplex form.

Despite the broad and varied scope of the organometallic art, nodisclosure is made of organometallic compounds which are substantive,and which can be modified with an active moiety to adapt the resultingcompound to a particular end use of choice. In addition, none of the artis directed to an organometallic compound which combines in a singlecompound both an amido carboxyl moiety and an active moiety.

Accordingly, it is a primary object of the present invention to providean organometallic compound which is substantive to various types ofsurfaces, and which contains an active moiety which may be selected froma wide variety of organic compounds, depending upon the particulardesired end use application of the organometallic compound. It is arelated object to provide an organometallic compound which issubstantive, includes an active moiety and is film-forming.

Another object of the present invention is to provide a substantiveorganometallic compound in which the relative degree of substantivitycan be varied.

A further object of this invention lies in the provision oforganometallic compounds which form films and which are substantive to awide variety of substrates.

Yet another object of this invention is to provide organometalliccompounds which are hydrophobic and in which the relative degree ofhydrophobicity can be varied.

It is a further object of the present invention to provide anorganometallic composition which is substantive to various types ofsurfaces, and which contains an active moiety which may be selected froma wide variety of organic compounds, depending upon the particulardesired end use application of the organometallic composition. A relatedobject is to provide an organometallic composition which is substantive,includes an active moiety and is film-forming.

Another object of this invention is to provide substantiveorganometallic compositions in which the relative degree ofsubstantivity can be varied. A further object is to provideorganometallic compositions which form films which are substantive to awide variety of substrates.

Another object of the present invention is to provide organometalliccompositions which are hydrophobic and in which the relative degree ofhydrophobicity can be varied.

Yet another object of this invention is to provide formulations whichinclude the substantive, active moiety-containing organometalliccompounds and/or organometallic compositions described herein.

These and other objects and advantages of the present invention will beapparent from the following description of the invention.

SUMMARY OF THE INVENTION

The present invention is predicated on the discovery that anorganometallic compound can be formed which includes both an amidocarboxyl moiety and an active moiety selected from a wide variety oforganic radicals capable of adapting the resulting compound to aparticular end use of choice. The organometallic compounds of thepresent invention are characterized by their substantivity and by theirvariable degrees of hydrophobicity. Desirably the organometalliccompounds of this invention will form a film when applied to asubstrate.

As used herein, the term film-forming means that the organometalliccompound, having been applied to a substrate, comprises a residual solidmaterial which is not chalky, and will not flake, granulate or form apowder, as typically occurs with organic compounds, such as, forexample, benzoic acid or the like, applied from an isopropyl alcoholsolution.

The organometallic compounds of this invention form films whichthemselves may or may not be continuous, but which have the appearanceof being continuous and will not fracture at random. The film so formedtypically remains intact, even if the substrate to which it is adheredis removed. The film thus appears to be polymeric in nature although theactual structure is not currently known.

While the organometallic compounds of this invention are soluble orsuspendable in the organic medium in which they are synthesized, whenapplied to a substrate and the solvent is removed, they form a solid,often a film, which will not readily redissolve or resuspend in likeorganic medium. The solid, or film, however, may decompose in a strongalkali solution.

The organometallic compounds of the present invention also displaysubstantivity to the surface to which they are applied. Substantivity,as used herein, means that the compound, when applied to a substrate,will adhere to the surface and is not readily removed by common solventssuch as water, acetone, alcohol and the like, nor can the compounds beeasily removed by mechanical action such as rubbing. The compounds ofthe present invention may be substantive to polar surfaces, non-polarsurfaces, or both, including, by way of illustration, and not inlimitation, human skin, fabric, wood, paper, teflon, steel, glass andthe like.

The organometallic compounds of the present invention comprise atrivalent or tetravalent metal, an amido carboxyl moiety bonded to themetal, an active moiety bonded to the metal and at least one modifiermoiety bonded to the metal, the number of such modifier moieties beingsufficient to satisfy the valency of the metal. The organometalliccompounds of the present invention are thus capable of combining thesubstantivity of the amido carboxyl metal system, functional efficacy ofan active moiety, and film-forming properties in a single compound.

The organometallic compounds of the present invention are useful in awide variety of applications. These compounds may find utility in anyfield or application where a degree of substantivity and/orhydrophobicity, combined with chemical, biological or physicalproperties of specific active moieties, are desired. Moreover, theorganometallic compounds of the present invention can be tailored to anyparticular end use application by appropriate selection of the activemoiety, the metal, the amido carboxyl moiety and the modifier moiety.

While the description herein is directed to the organometallic compoundsof the present invention, it should be understood that the descriptionis likewise applicable to the organometallic compositions described indetail hereinafter.

DETAILED DESCRIPTION OF THE INVENTION

The organometallic compounds of the present invention are described bythe general formula: ##STR1## wherein M is a trivalent or tetravalentmetal, R is an amido carboxyl moiety, R' is an active moiety, which mayalso be an amido carboxyl moiety, and R" is a modifier moiety capable ofsatisfying the valency of the metal, M. Depending upon the valency ofthe metal, n is either 1 or 2. More particularly, where the metal istrivalent, n is 1 and where the metal is tetravalent, n is 2.

Each moiety, R, R', R" and the metal M can affect the substantivity,film-forming character, hydrophobicity and functional activity of theorganometallic compounds of this invention. None of the properties ofthese compounds is solely dependent on any one moiety, although eachmoiety does not necessarily affect each property to the same degree.Accordingly, it is the interdependency of each of these moieties, R, R',R" and M, which must be taken into account to provide a compound whichnot only has the desired activity for the end use applicationcontemplated, but which will also have the film-forming characteristic,substantivity and hydrophobicity required to make the compound effectivefor that application.

Turning to the metal and moieties which comprise the organometalliccompounds of the present invention, the metal M may be a metal which hasa valency of at least three, trivalent and tetravalent metals beingpreferred. Suitable trivalent metals include aluminum and iron andsuitable tetravalent metals include tin, titanium, and zirconium.Aluminum, titanium, tin, and zirconium are preferred. Aluminum isparticularly preferred, because of its economy and non-toxicity.

The amido carboxyl moiety, R, may be saturated or unsaturated, aliphaticor aromatic. The preferred amido carboxyl moieties are those havingeither of the general formulas (a) or (b), whatever the derivation:##STR2##

In the amido carboxyl moieties described by formulas (a) and (b), theradicals R¹ and R² may be the same or different, and are selected fromthe group consisting of hydrogen, an alkyl radical of from 1 to about 20carbon atoms, an aryl, aralkyl, substituted aryl or substituted aralkylradical of from 6 to about 20 carbon atoms or an alkenyl radical of from3 to about 20 carbon atoms. The radicals R¹ and R² may be straightchain, branched, or substituted with halogen, hydroxyl and the like. Theradical, R³, in formulas (a) and (b) is a hydrocarbyl radical. The termhydrocarbyl radical as used herein means any carbon and hydrogencontaining radical, including aryl, aralkyl substituted aryl and aralkylradicals of from 6 to about 20 carbon atoms, alkyl and substituted alkylradicals of from 1 to about 20 carbon atoms, and alkenyl and substitutedalkenyl radicals of from 1 to about 20 carbon atoms. The radical, R³,preferably comprises a hydrocarbyl radical of from 1 to about 6 carbonatoms. The hydrocarbyl radical, R³, may be completely substituted withatoms such as halogen, as in, for example, the tetrabromophenyleneradical.

It is believed that the amido carboxyl-metal system contributes to thefilm-forming characteristic, substantivity and hydrophobicity of theorganometallic compounds of this invention. More particularly, it hasbeen found that each of the carbon chain lengths of the radicals, R¹, R²and R³, individually and collectively, may affect the properties of thefinal compound. Although the interrelationship of R¹, R² and R³ is notat present fully understood, it has been found that the chain length ofeach of R¹, R² and R³, and the total number of carbon atoms provided bythese radicals must be taken into account in order to provide a compoundwith the desired properties.

For example, with respect to the hydrophobicity of the organometalliccompounds, it has been found, generally, that if R¹ and R² are short,that is, the sum of the number of carbon atoms in R¹ and R² is less thanabout 4, then the compound is less hydrophobic than with longer chainlengths of R¹ and R², although substantivity appears to be satisfactory.On the other hand, as the chain length of each of R¹ and R², as well asthe total number of carbon atoms of R increases, the hydrophobicity ofthe organometallic compound increases, and the solubility in isopropylalcohol of the compound likewise increases. Substantivity, however, maydecrease. Solubility of the compound tends to decrease as the overallcarbon chain length of R exceeds about 12 to 15 carbon atoms or so. Thismay, for some compounds, affect film-forming and hydrophobicitydepending on the active moiety, R', and modifier moiety, R".

Organometallic compounds with as low as four carbon atoms in the amidocarboxyl moiety, R, have been found to have satisfactory substantivityand hydrophobicity. It is preferable that the total number of carbonatoms in R not be too large, however, or substantivity is notsatisfactory. It has been found that, in order for the organometalliccompounds of the present invention to have suitable hydrophobicity andsubstantivity for a given application, the radicals R¹ and R² must beindependently selected so that the sum of the carbon atoms in both R¹and R² is not greater than 40, and is preferably within the range of 4to 40, inclusive, and that the sum of the carbon atoms in the amidocarboxyl moiety, R, must be at least 4.

The degree of substitution on the nitrogen atoms of the amido carboxylmoiety has also been observed to affect both the hydrophobicity andsubstantivity of the organometallic compound. In general, it has beenfound that tertiary amido carboxyl moieties are more hydrophobic thansecondary amido carboxyl moieties, and at the same time are lesssubstantive, especially to glass, than secondary amido carboxylmoieties. It will thus be appreciated that there is substantialflexibility in selecting either or both of R¹ and R² depending upon therequirements of the end use. For example, if hydrophobicity is ofgreatest importance and substantivity is of less significance, atertiary amido carboxyl moiety may be employed as the R moiety.Conversely, if substantivity is of primary importance and hydrophobicityis less so, then a secondary amido carboxyl moiety may be employed asthe R radical.

It should further be appreciated that the active moiety R' may, to someextent, also affect the properties of the compound. Specifically, thehydrophobicity of the compound may be affected. Any such effect which R'may have, should accordingly be taken into account in selecting R¹, R²and R³.

It has been observed that the polarity of the active moiety, has aneffect on the properties of the organometallic compound. Generally, asthe polarity of the active moiety increases, the solubility of thecompound in polar organic solvents increases. Increased solubilitygenerally relates to improved film-forming and substantivity, but doesnot necessarily increase hydrophobicity.

Thus, in view of the substantial flexibility provided by theorganometallic compounds of the present invention it will be appreciatedthat some experimentation may be required in order to define the chainlength of R, and more particularly the desired chain length of each ofthe radicals R¹, R² and R³ for selected active moieties R', in order toachieve the overall desired properties of the final compound.

Amido carboxyl moieties corresponding to formula (a) above which havebeen found suitable for preparing the organometallic compounds of thepresent invention include amido carboxyl moieties derived from maleamicacid, phthalamic acid and succinamic acid. For maleamic acid derivedamido carboxyl moieties, R³ in the above formula is an ethenyleneradical, CH═CH. For phthalamic acid derived amido carboxyl moieties, R³in the above formula is a phenylene radical C₆ H₄. And, for succinamicacid derived amido carboxyl moieties, R³ in the above formula is anethylene radical, CH₂ CH₂. Preferred derivatives are dependent on R',the active moiety.

Illustrative of derivatives of succinamic acid which are suitable foruse in the present invention are:

N-dodecylsuccinamate, N-octylsuccinamate,

N-hexylsuccinamate, N-octadecylsuccinamate,

N-tetradecylsuccinamate, N-hexadecylsuccinamate,

N-propylsuccinamate, N-isopropylsuccinamate

N,N-dioctadecylsuccinamate, N,N-dipropylsuccinamate,

N-4-dodecylphenylsuccinamate, N-propyl-2-dodecenylsuccinamate,

and N,N-dilaurylsuccinamate.

Preferred derivatives are dictated by specific end use applications. Forexample, by way of illustration and not limitation, a derivative ofsuccinamic acid for an emollient application is N-tetradecylsuccinamate;a preferred derivative of succinamic acid for a sunscreen application isN-dodecylsuccinamate.

Illustrative of a suitable maleamic acid derivative isN-dodecylmaleamate. Illustrative of derivatives of phthalamic acid whichhave been found suitable are N-dodecylphthalamate andN-dodecyl-tetrabromophthalamate.

Amido carboxyl moieties corresponding to formula (b) above which havebeen found suitable for use in the organometallic compounds of thepresent invention include amido carboxyl moieties derived from sarcosineand proteins.

In sarcosine derived amido carboxyl moieties, R² is a methyl radical andR¹ is preferably a long chain fatty group. Exemplary of sarcosinederivatives which have been found suitable are cocoylsarcosine,oleoylsarcosine and lauroylsarcosine.

Preferred amido carboxyl moieties derived from naturally occurringproteins include acylated protein hydrolysates. Especially preferred isthe acylated protein hydrolysate made from Maypon®4C (a registeredtrademark of Inolex Chemical Company). Maypon®4C is identified by theCosmetic, Toiletry and Fragrance Association as potassium cocoahydrolyzed animal protein.

The active moiety, R', of the organometallic compounds of the presentinvention may be any moiety which enables the compound to perform aspecific chemical, biological or physical function. In one aspect theactive moiety may be derived from an organic compound which is itselfknown to be functionally efficacious for a selected end use, and whichmaintains its functional efficacy when bonded to the metal, such as, byway of example, an organic compound capable of absorbing ultravioletradiation. In another aspect, the active moiety may be derived from anorganic compound which is not necessarily functionally efficacious forthe selected end use, but which, when bonded to the amido carboxylmoiety-metal environment of the organometallic compounds of thisinvention, becomes effective for that purpose.

With respect to these aspects, it is contemplated that the active moietymay itself be a film former, or it may assist in the film-formingcharacteristic of the organometallic compound. In particular, it iswithin the scope of the present invention that R', the active moiety,can be an amido carboxyl moiety, R, as set forth above. Organometalliccompounds wherein both R and R' are amido carboxyl moieties have beenfound to have superior film-forming characteristics and substantivity.It is likewise contemplated that the amido carboxyl moiety may includeatoms, such as, for example, halogen, or other radicals, which mayimpart activity. Illustrative of an halogen containing amido carboxylmoiety is N-dodecyltetrabromophthalamate. Illustrative of other amidocarboxyl moieties which include an active group areN-tetradecylsuccinamate, N-hexadecylsuccinamate, N-dodecylsuccinamate,N-lauroylsarcosinate, N-cocoylsarcosinate, and N-oleylsarcosinate.

Any organic radical which is capable of bonding to the metal may besuitably employed as the active moiety. To promote facile bonding to themetal, the active moiety preferably contains an active (that is, acidic)hydrogen atom.

Typically, bonding of the active moiety R' to the metal may beaccomplished by a suitable organic linkage which may be a part of theactive moiety, such as, for example, a carboxylate, sulfonate,phosphate, phosphite, oxa, or thia linkage. It will be appreciated thatbonding of the modifier moiety, R", to the metal may likewise be throughsuch linkages.

Because of the wide variety of organic radicals which may be suitablyemployed as the active moiety, the organometallic compounds of thepresent invention may be tailored to a myriad of specific end useapplications. Broadly stated, the active moiety may be selected so as toprovide organometallic compounds suitable for use in such diverse fieldsand industries as cosmetics, industrial coatings, agriculture, textilesand leather, pharmaceuticals, photography, paint and ink, and plastics.

By appropriate selection of the active moiety, the organometalliccompounds of the present invention may be satisfactorily employed, forexample, in the following: in wood coatings, such as, for example,polishes, preservatives, waxes, waterproofing, ultraviolet absorber andthe like; in metal coatings such as polishes, corrosion inhibitors,sealers, paints and the like, and in paper products as a fire retardant,as a water proofer and the like; in textile and leather, including useas wrinkle reducers, flame retardants, sizing, waterproofing, sealing,permanent press, softener, mold release, antistat and the like; inagriculture, including herbicides, insecticides, insect repellants, seedprotectant and the like; in pharmaceutical uses, such as a liquidbandage or wound dressing, topical application of drugs, antisepticspray, encapsulating agent and the like; in cosmetics, including haircoloration, hair spray, hair conditioning, makeup, antiperspirant,perfume fixture, sunscreens, emollients and the like; in photography,including use as a support, overcoat, antistat, ultraviolet radiationabsorber, and the like; in paints and inks, such as, as an adhesive, anadditive or the like; and in plastics, such as a photocuring additive orultraviolet radiation absorber. Many other active moieties and end useswill be apparent to those skilled in the art.

Specific examples of active moieties and their intended application arediscussed below. These examples are illustrative of, and not inlimitation of, the active moieties that may find utility in theorganometallic compounds of the present invention. For example, asuitable example of a herbicide active moiety isα-2,4-dichlorophenoxyacetate; an example of an insect repellent activemoiety is monomethyl phthalate. Examples of ultra-violet absorbers usedas active moieties include p-dimethylaminobenzoate, p-aminobenzoate,urocanate, p-methoxycinnamate, salicylate and2-benzoyl-4-methoxyphenoxide.

Other types of active moieties include alkyl carboxylates having fromabout 6 to about 32 carbon atoms, unsaturated alkyl carboxylates,branched alkyl carboxylates and the like. The alkyl groups may besubstituted or perhalogenated.

Examples of active moieties capable of imparting emolliency to theorganometallic compounds of this invention include myristate, oleate,isostearate, 12-hydroxystearate, and carboxylates of dimer acids.

The organometallic compounds of the present invention further include atleast one modifier moiety, R", in order to satisfy the valency of themetal M. The number of modifier moieties required will, of course,depend upon the valency of the metal. Where the metal is trivalent, onlyone such modifier moiety will be required. Where the metal istetravalent, then two modifier moieties will be required. When twomodifier moieties are required, they may be the same or different. Forease of synthesis, it is preferable for both modifier moieties to be thesame. However, it will be appreciated that after synthesis, hydrolysismay occur, in whole or in part, so that the modifier moieties of theresulting compounds may be different. In general, mixtures of modifiermoieties are anticipated.

The modifier moiety, R", may be an hydroxyl, an alkoxy radical of from 1to about 6 carbon atoms, or a carboxyl radical of from 1 to about 6carbon atoms. The specific size of the modifier moiety, R", is ofprimary concern because of steric hindrance. For example, it is known tothe art that three stearate moieties will not bond to aluminum under thereaction conditions typically employed in the practice of the presentinvention. Accordingly, hydroxyl, or some other group, including alkoxyradicals of from 1 to about 3 carbon atoms, and carboxyl radicals offrom 1 to about 3 carbon atoms are preferred.

The specific composition of the modifier moiety, R", has been found toappreciably affect the properties of the organometallic compounds of thepresent invention. There is a direct relationship between the polarnature of an organic modifier moiety and the solubility of theorganometallic compound in organic media, such as isopropyl alcohol,such that, as the polarity of R" increases, the solubility of theorganometallic compound likewise increases. However, when R" ishydroxyl, the compounds are less soluble in alcohol and the film-formingcharacteristics, and substantivity of the organometallic compounds isgenerally diminished. It has also been observed that, generally, wherethe modifier moiety is a lower alkyl carboxylate radical, and, inparticular acetate or lactate, the substantivity of the organometalliccompound is improved. The effect of the modifier moiety on theproperties of the organometallic compound of the present invention isillustrated in the examples. It has thus been observed thatorganometallic compounds, identical in all respects except for themodifier moiety, have different film-forming characteristics,substantivity and hydrophobicity. Where the metal is aluminum, titaniumor zirconium, the modifier moiety R" is preferably an hydroxyl, anisopropoxyl, an n-propoxyl, an acetate or a lactate radical. In the caseof tin, the modifier moiety R" is preferably a lower alkyl radical offrom 1 to about 6 carbon atoms, preferably of from 1 to about 4 carbonatoms. The n-butyl radical is especially preferred.

With some organometallic compounds of the present invention, it has beenobserved that the desirable properties of the active moiety have beenenhanced by their being bonded to the metal. Particularly, this has beenobserved in the preparation of emollients. For example, myristic acidis, itself, a poor emollient. However myristate, as the active moiety inthe organometallic compounds described herein, resulted in a compoundwhich has emollient properties which are superior to those of myristicacid.

Organometallic compounds of the present invention suitable for sunscreenapplications, includeN-dodecylsuccinamate-p-dimethylaminobenzoatealuminum isopropylate,N-oleoylsarcosinate-p-dimethylaminobenzoatezirconium bis-n-propylate, orN-octylsuccinamate-p-aminobenzoatedibutyltin.

Formulations into which the organometallic compounds of this inventionmay be incorporated, as for example, a cosmetic formulation or the like,exhibit desirable properties. As an illustration, improved efficacy mayresult because the active moiety is held to the substrate. In addition,product design flexibility is enhanced because of the wide variety ofactive moieties that may be used to make the organometallic compound.

In accordance with another aspect of the present invention, acomposition comprising a mixture or mixtures of the organometalliccompounds described in detail herein above is anticipated. Theorganometallic compositions of the present invention may thus includeorganometallic compounds in which R and R' are the same or different,including, for example, organometallic compounds which comprise two ormore active moieties, R', bonded to the metal, and organometalliccompositions which comprise two or more amido carboxyl moieties, R,bonded to the metal. More particularly, organometallic compositions arecontemplated which have the formula ##STR3## wherein M, R, R' and R"represent materials or mixtures of materials selected from the groupcomprising respectively, trivalent or tetravalent metals, amido carboxylmoieties, active moieties and modifier moieties, and are the same,respectively, as they are for the organometallic compounds describedabove. In this formula x and y are each greater than 0 and equal to orless than 2, the sum of x and y is less than z, and z is the valency ofthe metal.

The general formula of the organometallic compositions of the presentinvention set forth above is not intended to indicate the actualstructure of any organometallic composition, but is, instead, intendedto indicate the average stoichiometry between the metal M and themoieties R, R' and R". Preferred compositions are those wherein thestoichiometry is such that x is from 0.5 to 1.5 and y is from 0.5 to1.5; and most preferably those in which, x and y are each about one.

It will be appreciated to those skilled in the metallosoap art thatthere are many synthetic routes which may be utilized in order to makethe organometallic compounds and compositions of the present invention.

As one example, synthesis of the organometallic compounds andcompositions of the present invention comprises the reaction of anorganometallic starting material with the appropriate active hydrogencontaining compounds to effect substitution at the metal with,respectively, the amido carboxyl moieties, active moieties and modifiermoieties of choice. For organometallic compositions of the presentinvention in which the metal is aluminum, zirconium or titanium, it ispreferred to use a metalalkoxide starting material. Specifically, forthe organoaluminum compounds, the preferred starting material isaluminum isopropoxide. For the organozirconium compounds, the preferredstarting material is zirconium tetra-n-propoxide. For the organotitaniumcompounds, the preferred starting material is titaniumtetraisopropoxide.

One reaction sequence which may be followed to provide theorganometallic compounds and compositions of this invention can bedescribed as follows: ##STR4##

Optionally, the organometallic composition of step (2) may be furtherreacted, in whole or in part, to produce compositions where R" isdifferent from that in the starting material as, for example, as shownbelow in the case of water: ##STR5## where w is greater than 0 and equalto or less than z-(x+y).

While there are other synthetic routes which should be apparent to thoseskilled in the art that may be used in preparing the compositions ofthis invention, the synthetic route described above is preferred becauseit allows for the greatest flexibility in the R, R' and R" moieties ofthe final product. By way of example, the stoichiometry of the reactionsynthesis can be suitably selected to provide a composition in which Rmay be a single amido carboxyl moiety or a mixture of amido carboxylmoieties, and/or R' may be a single active moiety or a mixture of activemoieties, and/or R" may be a single modifier moiety or a mixture ofmodifier moieties. Further, the modifier moiety of the final compositioncan be changed in whole or in part by subsequent reaction of thecomposition with a second modifier moiety as shown in equation (3). Forexample, if the starter is aluminum isopropoxide, R" in the finalproduct will be isopropoxide in equation (2) (R" may also be hydroxidedue to hydrolysis of the isopropoxide, equation (3)). The isopropoxylcontaining composition may be reacted with a lower alkyl carboxylicacid, such as, for example, acetic acid, in order to substitute theisopropoxyl radical with a lower alkyl carboxylate (acetate).

For organotin compositions of the present invention, the preferredstarting material is an alkyltin oxide, and the resulting compositionhas the general formula: ##STR6## wherein R is the amido carboxylmoiety, R' is the active moiety, R" is an alkyl radical and x and y areeach greater than 0 and less than 2, and the sum of x and y is greaterthan 1 and less than or equal to 2.

In a synthesis of organotin compositions in accordance with the presentinvention, a dialkyltin oxide, preferably dibutyltin oxide, is reactedsequentially with the active hydrogen containing organic compounds, forexample, where x and y are each equal to one, by the following syntheticroute: ##STR7##

In preparing organotin compositions of the present invention, hydroxylradicals may be substituted, in whole or in part, with an active moietyor modifier moiety, by a reaction with an active hydrogen containingorganic compound. For example, reaction of the hydroxyl with a loweralkyl carboxylate may be readily accomplished.

DEFINITIONS

As used in the Examples appearing below, the following designations,symbols, terms and abbreviations have the indicated meanings:

Maypon®4C denotes cocoa hydrolyzed animal protein, derived from theprotein salt commercially available from Inolex Chemical Company, afterreaction with the organometallic starting material;

Bio-Soft®S-100 (a registered trademark of Stepan Company) denotesdodecylbenzenesulfonic acid, after reaction with the organometallicstarting material;

DMPABA denotes p-dimethylaminobenzoic acid, after reaction with theorganometallic starting material;

PABA denotes p-aminobenzoic acid, after reaction with the organometallicstarting material;

Hamposyl®C denotes cocoylsarcosine, commercially available from W.R.Grace & Co., after reaction with the organometallic starting material;

Hamposyl®L denotes lauroylsarcosine, commercially available from W.R.Grace & Co., after reaction with the organometallic starting material;

Hamposyl®O denotes oleoylsarcosine, commercially available from W.R.Grace & Co., after reaction with the organometallic starting material;

FF denotes film-forming property;

SUB denotes substantivity; and

HPB denotes hydrophobicity.

PROCEDURES

The following test procedures were employed to evaluate theorganometallic compounds and compositions of the present invention.

SUBSTANTIVITY AND FILM-FORMING TEST

A substantivity and film-forming test was developed in order tocharacterize the organometallic compounds of this invention and toprovide a standard for comparing them.

The following procedure was used in carrying out the film-forming test:

A 1"×3" glass microscope slide was dipped into a 7% isopropyl alcoholsolution/slurry of the organometallic compound to be tested. Theseslides were allowed to dry for thirty minutes. If a thick film resulted,the compound was wiped to a thin film of less than 3 mils in thicknessbefore it dried for the test.

Each material was then graded in three separate categories, namelyfilm-forming property, hydrophobicity and substantivity. The criteriaused in each category are set out below:

A. Film-Forming Property. The film-forming characteristic or property ofthe organometallic compounds were graded as follows:

+continuous uniform film

o continuous nonuniform film

-not continuous, nonuniform; "spotty",

powdery, or "chalky" in appearance.

B. Hydrophobicity. The hydrophobicity of the film was determined byrunning 55° C. tap water over the coated plates for sixty seconds. Thematerial on the plates was then graded by visual observation as follows:

+75-100% of the material remains on the plate.

o 50-75% of the material remains on the plate.

-50% of the material remains on the plate.

C. Substantivity. The substantivity of the film was graded as follows:

+Material cannot be removed or can only be removed with very forcefulrubbing.

o Material can be removed with rubbing, but displays some adhesiveproperties.

-Material is readily removed with rubbing.

A substantivity of "o" or "+" denotes that the resulting material issubstantive as that term is defined herein.

The following examples are illustrative of and not in limitation of thisinvention.

EXAMPLE 1

This Example illustrates the preparation ofN-dodecylsuccinamate-p-dimethylaminobenzoatealuminum isopropylate. Theactive moiety absorbs ultraviolet radiation, and the composition is thussuitable for use as a sunscreen.

Aluminum isopropoxide, (0.044 mole, 8.97 grams) was placed in a oneliter, four-neck, round bottom flask fitted with a mechanical stirrer,an Allihn condenser, nitrogen sparge, and an addition funnel. Dryisopropyl alcohol, 143 ml, was added and the mixture stirred andrefluxed for fifteen minutes. The addition funnel was charged withN-dodecylsuccinamic acid (0.044 mole, 12.54 grams) dissolved in 50 mlisopropyl alcohol. The N-dodecylsuccinamic acid solution was addedslowly, over twenty minutes, to the refluxing aluminum isopropoxidesolution. Refluxing was continued for one hour andp-dimethylaminobenzoic acid (0.044 mole, 7.26 grams) dissolved in 167 mlof hot isopropyl alcohol, was added all at once. After an additional twohour reflux, three-fourths of the reaction mixture was allowed to coolto room temperature; the remaining one-fourth was treated as describedbelow. A fine, white suspension was obtained and characterized by IR andproton NMR analyses.

The fine white suspension so obtained was found to be substantive toskin, it did not wash off with water, and showed an enhancement in theUV spectrum.

This compound was graded as follows:

film-forming property: +

substantivity: o

hydrophobicity: +.

The remaining one-fourth of the reactive mixture produced above wasreacted with water to convert a portion of the isopropylate to hydroxyl,as follows.

Before the reaction mixture was allowed to cool, 0.011 mole of water wasadded to the mixture all at once. The resulting mixture was thenrefluxed for an additional 15 minutes. It was found that about 70% ofthe N-dodecylsuccinamate-p-dimethylaminobenzoate aluminumisopropylatewas converted to N-dodecylsuccinamate-p-dimethylaminobenzoatealuminum-hydroxide.

In like fashion, the modifier moiety, R", can be converted to acarboxylate by appropriate reaction with a carboxylic acid.

EXAMPLE 2

This Example illustrates the preparation of Maypon®4C myristatealuminumhydroxide, which is suitable for use as an emollient.

Octylisononanoate, 39.4 grams, and Maypon®4C acids (41% solids inisopropyl alcohol, 68.9 grams), were placed in a 250 ml beaker fittedwith a magnetic stirrer. The isopropyl alcohol was removed by heatingthe mixture to 105° C. Aluminum isopropylate cyclic trimer (12.3%aluminum content in isopropyl palmitate, 14.3 grams) was then added allat once. The reaction mixture was heated at 93° C for one hour. Myristicacid (14.7 grams) was added and the reaction allowed to stir at 93° Cfor one hour. The final product is a clear, viscous liquid.

EXAMPLES 3-130

Examples 3-130 illustrate various organoaluminum compounds of thepresent invention. These compounds were made in accordance with theprocedure of Example 1. The compounds have the formula: ##STR8##

The specific amido carboxyl moiety, active moiety and modifier moiety ofthe compounds, as well as the film-forming characteristics,hydrophobicity and substantivity (according to the procedures set forthabove) for these compounds, are set forth in Table I:

                                      TABLE I                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              R              R'          R"    FF SUB                                                                              HPB                                 __________________________________________________________________________    3  succinamate    PABA        hydroxyl                                                                            -  -  o                                   4  succinamate    PABA        acetate                                                                             -  o  o                                   5  N--propylsuccinamate                                                                         DMPABA      hydroxyl                                                                            +  +  -                                   6  N--propylsuccinamate                                                                         DMPABA      acetate                                                                             +  +  -                                   7  N--propylsuccinamate                                                                         PABA        hydroxyl                                                                            o  o  -                                   8  N--propylsuccinamate                                                                         benzoate    hydroxyl                                                                            +  +  -                                   9  N--propylsuccinamate                                                                         benzoate    acetate                                                                             +  +  -                                   10 N--propylsuccinamate                                                                         pyruvate    hydroxyl                                                                            +  +  o                                   11 N--propylsuccinamate                                                                         pyruvate    acetate                                                                             +  +  -                                   12 N--hexylsuccinamate                                                                          DMPABA      hydroxyl                                                                            o  +  -                                   13 N--hexylsuccinamate                                                                          DMPABA      acetate                                                                             +  +  -                                   14 N--hexylsuccinamate                                                                          PABA        hydroxyl                                                                            -  o  +                                   15 N--hexylsuccinamate                                                                          PABA        acetate                                                                             -  +  +                                   16 N--hexylsuccinamate                                                                          PABA        isopropoxyl                                                                         o  o  o                                   17 N--hexylsuccinamate                                                                          benzoate    hydroxyl                                                                            o  +  -                                   18 N--hexylsuccinamate                                                                          benzoate    acetate                                                                             +  +  o                                   19 N--hexylsuccinamate                                                                          pyruvate    hydroxyl                                                                            +  +  +                                   20 N--hexylsuccinamate                                                                          pyruvate    acetate                                                                             +  +  +                                   21 N--octylsuccinamate                                                                          DMPABA      hydroxyl                                                                            +  +  -                                   22 N--octylsuccinamate                                                                          DMPABA      acetate                                                                             +  +  +                                   23 N--octylsuccinamate                                                                          PABA        hydroxyl                                                                            o  o  +                                   24 N--octylsuccinamate                                                                          benzoate    hydroxyl                                                                            -  o  +                                   25 N--octylsuccinamate                                                                          benzoate    acetate                                                                             o  +  +                                   26 N--octylsuccinamate                                                                          pyruvate    hydroxyl                                                                            +  +  +                                   27 N--octylsuccinamate                                                                          pyruvate    acetate                                                                             +  +  +                                   28 N--dodecylsuccinamate                                                                        DMPABA      hydroxyl                                                                            +  o  +                                   29 N--dodecylsuccinamate                                                                        DMPABA      acetate                                                                             +  o  +                                   30 N--dodecylsuccinamate                                                                        DMPABA      lactate                                                                             o  +  o                                   31 N--dodecylsuccinamate                                                                        PABA        hydroxyl                                                                            -  o  +                                   32 N--dodecylsuccinamate                                                                        PABA        acetate                                                                             +  +  +                                   33 N--dodecylsuccinamate                                                                        PABA        isopropoxyl                                                                         -  o  +                                   34 N--dodecylsuccinamate                                                                        benzoate    hydroxyl                                                                            +  o  +                                   35 N--dodecylsuccinamate                                                                        benzoate    acetate                                                                             +  +  +                                   36 N--tetradecylsuccinamate*                                                                    DMPABA      hydroxyl                                                                            -  -  +                                   37 N--tetradecylsuccinamate*                                                                    DMPABA      acetate                                                                             -  -  +                                   38 N--tetradecylsuccinamate                                                                     DMPABA      lactate                                                                             +  o  o                                   39 N--tetradecylsuccinamate*                                                                    PABA        hydroxyl                                                                            -  -  +                                   40 N--tetradecylsuccinamate*                                                                    PABA        acetate                                                                             -  -  o                                   41 N--tetradecylsuccinamate                                                                     PABA        lactate                                                                             +  +  o                                   42 N--tetradecylsuccinamate*                                                                    benzoate    hydroxyl                                                                            +  -  +                                   43 N--tetradecylsuccinamate                                                                     benzoate    acetate                                                                             o  o  +                                   44 N--tetradecylsuccinamate                                                                     benzoate    lactate                                                                             +  +  o                                   45 N--tetradecylsuccinamate                                                                     pyruvate    hydroxyl                                                                            +  o  +                                   46 N--tetradecylsuccinamate                                                                     pyruvate    acetate                                                                             o  +  +                                   47 N--tetradecylsuccinamate                                                                     pyruvate    lactate                                                                             o  +  -                                   48 N--hexadecylsuccinamate*                                                                     DMPABA      hydroxyl                                                                            -  -  +                                   49 N--hexadecylsuccinamate                                                                      DMPABA      acetate                                                                             -  -  +                                   50 N--hexadecylsuccinamate                                                                      DMPABA      lactate                                                                             +  +  +                                   51 N--hexadecylsuccinamate*                                                                     PABA        acetate                                                                             -  -  +                                   52 N--hexadecylsuccinamate                                                                      PABA        lactate                                                                             +  +  +                                   53 N--hexadecylsuccinamate*                                                                     benzoate    hydroxyl                                                                            -  -  +                                   54 N--hexadecylsuccinamate                                                                      benzoate    acetate                                                                             o  o  +                                   55 N--hexadecylsuccinamate                                                                      benzoate    lactate                                                                             -  o  -                                   56 N--hexadecylsuccinamate*                                                                     pyruvate    hydroxyl                                                                            -  -  +                                   57 N--hexadecylsuccinamate                                                                      pyruvate    acetate                                                                             +  +  +                                   58 N--hexadecylsuccinamate                                                                      pyruvate    lactate                                                                             -  +  -                                   59 N--octadecylsuccinamate                                                                      DMPABA      hydroxyl                                                                            -  -  +                                   60 N--octadecylsuccinamate                                                                      DMPABA      acetate                                                                             +  o  +                                   61 N--octadecylsuccinamate                                                                      PABA        hydroxyl                                                                            +  o  +                                   62 N--octadecylsuccinamate                                                                      benzoate    hydroxyl                                                                            o  -  +                                   63 N--octadecylsuccinamate                                                                      benzoate    acetate                                                                             +  o  +                                   64 Hamposyl ® C                                                                             PABA        hydroxyl                                                                            +  o  o                                   65 Hamposyl ® C                                                                             PABA        acetate                                                                             -  +  -                                   66 Hamposyl ® L                                                                             PABA        hydroxyl                                                                            +  o  +                                   67 Hamposyl ® L                                                                             PABA        acetate                                                                             +  +  +                                   68 Hamposyl ® O                                                                             PABA        hydroxyl                                                                            +  o  +                                   69 Hamposyl ® O                                                                             PABA        acetate                                                                             -  +  o                                   70 Maypon ® 4C                                                                              DMPABA      hydroxyl                                                                            +  o  +                                   71 Maypon ® 4C                                                                              PABA        hydroxyl                                                                            +  +  -                                   72 6-acetamidohexanoate                                                                         PABA        hydroxyl                                                                            -  o  -                                   73 N--acetylglycine                                                                             DMPABA      hydroxyl                                                                            -  -  -                                   74 N--acetylglycine                                                                             DMPABA      acetate                                                                             o  o  -                                   75 N--propyl-2-dodec-                                                                           DMPABA      acetate                                                                             +  +  +                                      enylsuccinamate                                                            76 N--propyl-2-dodec-                                                                           DMPABA      hydroxyl                                                                            o  o  +                                      enylsuccinamate                                                            77 N,N--dipropylsuccinamate                                                                     DMPABA      hydroxyl                                                                            +  o  +                                   78 N,N--dipropylsuccinamate                                                                     DMPABA      acetate                                                                             +  o  -                                   79 N,N--dipropylsuccinamate                                                                     PABA        hydroxyl                                                                            o  +  +                                   80 N,N--dipropylsuccinamate                                                                     benzoate    hydroxyl                                                                            o  +  o                                   81 N,N--dipropylsuccinamate                                                                     benzoate    acetate                                                                             +  +  +                                   82 N,N--didodecylsuccinamate                                                                    DMPABA      hydroxyl                                                                            -  -  +                                   83 N,N--didodecylsuccinamate                                                                    DMPABA      acetate                                                                             o  o  +                                   84 N,N--didodecylsuccinamate                                                                    PABA        acetate                                                                             +  o  +                                   85 N,N--didodecylsuccinamate                                                                    benzoate    hydroxyl                                                                            -  -  +                                   86 N,N--didodecylsuccinamate                                                                    benzoate    acetate                                                                             -  o  +                                   87 N,N--dioctadecylsuccinamate                                                                  DMPABA      hydroxyl                                                                            -  -  -                                   88 N,N--dioctadecylsuccinamate                                                                  DMPABA      acetate                                                                             +  +  +                                   89 N,N--dioctadecylsuccinamate                                                                  PABA        hydroxyl                                                                            o  -  -                                   90 N,N--dioctadecylsuccinamate                                                                  benzoate    hydroxyl                                                                            -  -  +                                   91 N,N--dioctadecylsuccinamate                                                                  benzoate    acetate                                                                             +  +  +                                   92 N--dodecylsuccinamate                                                                        Bio Soft ® S-100                                                                      hydroxyl                                                                            +  o  +                                   93 N--dodecylsuccinamate                                                                        Bio Soft ® S-100                                                                      acetate                                                                             +  o  +                                   94 N--dodecylsuccinamate                                                                        bishexadecylphos-                                                                         hydroxyl                                                                            +  o  +                                                     phate                                                       95 N--dodecylsuccinamate                                                                        diethylphosphate                                                                          hydroxyl                                                                            o  -  +                                   96 N--dodecylsuccinamate                                                                        diethylphosphate                                                                          acetate                                                                             +  +  +                                   97 N--dodecylsuccinamate                                                                        dodecanthiol                                                                              hydroxyl                                                                            -  -  +                                   98 N--dodecylsuccinamate                                                                        octoxide    hydroxyl                                                                            +  +  +                                   99 N--dodecylsuccinamate                                                                        octoxide    acetate                                                                             +  +  +                                   100                                                                              Maypon ® 4C                                                                              methylsulfate                                                                             hydroxyl                                                                            +  +  +                                   101                                                                              N--octylsuccinamate                                                                          acetylsalicylate                                                                          acetate                                                                             +  +  +                                   102                                                                              N--octylsuccinamate                                                                          acetylsalicylate                                                                          isopropoxyl                                                                         +  +  +                                   103                                                                              N--dodecylsuccinamate                                                                        2,2'-dihydroxy-4,4'-                                                                      hydroxyl                                                                            o  +  +                                                     dimethoxybenzo-                                                               phenone                                                     104                                                                              N--dodecylsuccinamate                                                                        2,2'-dihydroxy-4,4'-                                                                      acetate                                                                             o  +  +                                                     dimethoxybenzo-                                                               phenone                                                     105                                                                              N--dodecylsuccinamate                                                                        2,4-dichlorophenoxy-                                                                      hydroxyl                                                                            +  +  +                                                     acetate                                                     106                                                                              N--dodecylsuccinamate                                                                        2,4-dichlorophenoxy-                                                                      acetate                                                                             +  +  +                                                     acetate                                                     107                                                                              N--dodecylsuccinamate                                                                        acetylsalicylate                                                                          hydroxyl                                                                            +  +  +                                   108                                                                              N--dodecylsuccinamate                                                                        acetylsalicylate                                                                          acetate                                                                             +  +  +                                   109                                                                              N--dodecylsuccinamate                                                                        ascorbate   hydroxyl                                                                            +  +  -                                   110                                                                              N--dodecylsuccinamate                                                                        ascorbate   acetate                                                                             +  +  -                                   111                                                                              N--dodecylsuccinamate                                                                        ascorbate   isopropoxyl                                                                         +  +  -                                   112                                                                              Maypon ® 4C                                                                              2-acetoylbenzoate                                                                         hydroxyl                                                                            +  +  -                                   113                                                                              Maypon ® 4C                                                                              4-methoxycinnamate                                                                        hydroxyl                                                                            +  +  -                                   114                                                                              Maypon ® 4C                                                                              laurate     hydroxyl                                                                            +  o  +                                   115                                                                              Maypon ® 4C                                                                              uraconate   hydroxyl                                                                            +  +  -                                   116                                                                              Maypon ® 4C                                                                              monomethylphthalate                                                                       isoproxyl                                                                           +  +  -                                   117                                                                              Hamposyl ® L                                                                             myristate   hydroxyl                                                                            +  +  +                                   118                                                                              N--dodecylphthalate                                                                          DMPABA      hydroxyl                                                                            +  o  +                                   119                                                                              N--dodecylphthalate                                                                          DMPABA      hydroxyl                                                                            +  -  -                                   120                                                                              N--octylsuccinamate                                                                          lactate     lactate                                                                             +  o  +                                   121                                                                              N--octylsuccinamate                                                                          N--octylsuccinamate                                                                       hydroxyl                                                                            +  +  +                                   122                                                                              N--octylsuccinamate                                                                          N--octylsuccinamate                                                                       acetate                                                                             +  +  +                                   123                                                                              N--dodecylsuccinamate                                                                        N--dodecylsuccinamate                                                                     hydroxyl                                                                            +  +  +                                   124                                                                              N--dodecylsuccinamate                                                                        N--dodecylsuccinamate                                                                     acetate                                                                             +  +  +                                   125                                                                              N--tetradecylsuccinamate                                                                     N--tetradecyl-                                                                            hydroxyl                                                                            +  o  +                                                     succinamate                                                 126                                                                              N--tetradecylsuccinamate                                                                     N--tetradecyl-                                                                            acetate                                                                             +  o  +                                                     succinamate                                                 127                                                                              Hamposyl ® C                                                                             Hamposyl ® C                                                                          hydroxyl                                                                            +  +  +                                   128                                                                              N--dodecyltetrabromo-                                                                        N--dodecyltetrabromo-                                                                     isopropoxyl                                                                         o  +  +                                      phthalamate    phthalamate                                                 129                                                                              N--tetradecylsuccinamate                                                                     N--tetradecyl-                                                                            lactate                                                                             +  o  +                                                     succinamate                                                 130                                                                              Maypon ® 4C                                                                              Maypon ® 4C                                                                           hydroxyl                                                                            +  +  +                                   __________________________________________________________________________     *In these Examples, the hydroxyl content of the aluminum isopropylate was     very high, and it is believed that the high hydroxyl content had an           adverse effect on substantivity, as illustrated. However, it is further       believed that with an aluminum isopropylate starting material with lower      hydroxyl content that compounds having the desired substantivity would        result.                                                                  

The data in Table I demonstrates the effect that each of the amidocarboxyl moiety, active moiety and modifier moiety may have on theproperties of the organometallic compounds and compositions of thepresent invention and illustrates that the interdependency of thesemoieties must be taken into account in order to provide a compound orcomposition which not only has the desired activity for the contemplatedend use, but which will also have the film-forming characteristic,substantivity and hydrophobicity to make the compound effective for thatapplication.

For example, Examples 1-63 illustrate the effect of chain length of theamido carboxyl moiety on the film-forming property, substantivity andhydrophobicity of the organometallic compounds. In general, as thecarbon chain length increases, substantivity decreases, although it isstill satisfactory in most cases, while hydrophobicity increases.However, the modifier moiety can have significant effect on bothsubstantivity and hydrophobicity, as illustrated in, for example,Examples 3 and 4, 14-16 and 28-30. Similarly, the effect of the polarityof the active moiety can also be seen from Examples 1-63. Generally, thegreater the polarity of the active moiety, the greater the substantivityof the organometallic compounds and compositions. Further, Examples 5-91illustrate the effect of a secondary versus tertiary amido carboxylmoiety. It can be seen that generally tertiary amido carboxyl moietiesare more hydrophobic, but less substantive than secondary amido carboxylmoieties .

These Examples in general, and Examples 92-106 in particular, illustratethe wide variety of linkages on the active moiety through which bondingof the active moiety to the metal may be accomplished. Exemplary of thewide variety of active moieties that may be incorporated in theorganometallic compounds of this invention are the compounds shown inExamples 101-120. Examples 121-130 illustrate organometallic compoundswherein the active moiety is itself a filmformer. As can be seen, thesecompounds exhibit superior film-forming characteristics.

Examples 118-119 illustrate the effect of the presence of water duringthe synthesis of the compounds of this invention. The product of Example119 was made in the presence of excess water and the effect onsubstantivity and hydrophobicity can be seen when compared with Example118.

EXAMPLE 131

This Example illustrates the preparation of Maypon®4Cp-aminobenzoatetitanium diisopropoxide, which is useful as a sunscreen.

Titanium tetraisopropoxide (0.044 mole, 12.5 grams) in 143 ml ofisopropyl alcohol was refluxed for fifteen minutes in a one liter,four-neck, round bottom flask fitted with a mechanical stirrer, anAllihn condenser, an addition funnel, and a nitrogen sparge. Maypon 4Cacids (42.00 grams; 45.4% solids in IPA; 443 grams/mole, 0.044 mole) wasadded over a fifteen minute period to the refluxing solution. After onehour reflux, p-aminobenzoic acid (0.044 mole, 6.04 grams) in 169 ml ofisopropyl alcohol was added all at once. The reaction mixture wasrefluxed for an additional two hours and cooled to room temperature. Thebright orange solution gave an IR typical of a metal soap.

This compound was graded as follows:

film-forming property: +

substantivity: +

hydrophobicity: o.

EXAMPLE 132

This Example illustrates the preparation ofoctylsuccinamate-p-aminobenzoatedibutyltin. The active moiety is anultraviolet absorber and the composition is useful as a sunscreen.

Dibutyltin oxide (0.25 mole, 62.2 grams) in 300 ml dry benzene wasplaced in a 500 ml round bottom flask fitted with a magnetic stirrer, aDean-Stark trap, and nitrogen sparge. Octylsuccinamic acid (0.25 mole,57.3 grams) in 100 ml benzene, was added slowly to the refluxing mixtureand the hazy suspension became clear. p-Aminobenzoic acid (0.25 mole,34.3 grams) was added all at once and the reaction mixture refluxed forfour hours. The benzene was removed in vacuum and the oil productcharacterized by IR and proton NMR.

This compound was graded as follows:

film-forming: +

substantivity: +

hydrophobicity: +.

EXAMPLE 133

This Example illustrates the preparation ofoleoylsarcosinate-p-dimethylaminobenzoatezirconium bisn-propylate, whichis useful as a sunscreen.

In a reaction vessel similar to that used in Example 1, zirconiumtetrapropoxide (0.044 mole, 14.41 grams) in 143 ml of isopropyl alcoholwas refluxed for fifteen minutes. Through the addition funnel,oleoylsarcosine (0.044 mole, 15.40 grams) in 50 ml of isopropyl alcoholwas added over a fifteen minute period. After the mixture was refluxedfor one hour, p-dimethylaminobenzoic acid (0.044 mole, 7.27 grams) in163 ml of isopropyl alcohol was added all at once. The reaction mixturewas refluxed an additional two hours and cooled to room temperature. Theproduct was characterized by IR, UV, proton NMR analyses.

This compound was graded as follows:

film-forming: +

substantivity: o

hydrophobicity: +.

EXAMPLES 134-168

These Examples illustrate the preparation of organozirconium compoundswith a wide variety of active and modifier moieties. These compoundswere prepared in accordance with the procedure of Example 133.

The compounds have the general formula: ##STR9##

The specific amido carboxyl moiety, active moiety and modifier moiety ofthe compounds, as well as the film-forming characteristic,hydrophobicity and substantivity (according to the procedures set forthabove) for these compounds are set forth in Table II.

                                      TABLE II                                    __________________________________________________________________________    Ex.                                                                           No.                                                                              R            R'          R"   FF SUB                                                                              HPB                                    __________________________________________________________________________    134                                                                              N--propylsuccinamate                                                                       DMPABA      hydroxyl                                                                           -  o  +                                      135                                                                              N--propylsuccinamate                                                                       DMPABA      acetate                                                                            -  o  +                                      136                                                                              N--propylsuccinamate                                                                       DMPABA      propoxyl                                                                           -  o  -                                      137                                                                              N--isopropylsuccinamate                                                                    DMPABA      hydroxyl                                                                           +  o  +                                      138                                                                              N--isopropylsuccinamate                                                                    DMPABA      acetate                                                                            o  o  +                                      139                                                                              N--hexylsuccinamate                                                                        DMPABA      hydroxyl                                                                           +  o  +                                      140                                                                              N--hexylsuccinamate                                                                        DMPABA      acetate                                                                            +  o  +                                      141                                                                              N--hexylsuccinamate                                                                        DMPABA      propoxyl                                                                           +  o  +                                      142                                                                              N--octylsuccinamate                                                                        DMPABA      hydroxyl                                                                           +  +  +                                      143                                                                              N--octylsuccinamate                                                                        DMPABA      acetate                                                                            +  +  +                                      144                                                                              N--octylsuccinamate                                                                        DMPABA      propoxyl                                                                           +  +  +                                      145                                                                              N--dodecylsuccinamate                                                                      DMPABA      hydroxyl                                                                           +  o  +                                      146                                                                              N--dodecylsuccinamate                                                                      DMPABA      acetate                                                                            +  o  +                                      147                                                                              N--dodecylsuccinamate                                                                      DMPABA      lactate                                                                            +  +  +                                      148                                                                              N--dodecylsuccinamate                                                                      DMPABA      propoxyl                                                                           +  o  +                                      149                                                                              N--dodecylsuccinamate                                                                      salicylate  propoxyl                                                                           +  o  +                                      150                                                                              N--octadecylsuccinamate                                                                    DMPABA      hydroxyl                                                                           -  -  o                                      151                                                                              N--octadecylsuccinamate                                                                    DMPABA      acetate                                                                            -  -  +                                      152                                                                              N--octadecylsuccinamate                                                                    DMPABA      propoxyl                                                                           -  -  o                                      153                                                                              Hamposyl ® C                                                                           DMPABA      hydroxyl                                                                           +  o  +                                      154                                                                              Hamposyl ® C                                                                           DMPABA      acetate                                                                            +  o  +                                      155                                                                              Hamposyl ® C                                                                           DMPABA      lactate                                                                            o  o  +                                      156                                                                              Hamposyl ® C                                                                           DMPABA      propoxyl                                                                           o  o  +                                      157                                                                              Hamposyl ® L                                                                           DMPABA      acetate                                                                            +  o  +                                      158                                                                              Hamposyl ® L                                                                           DMPABA      lactate                                                                            +  o  +                                      159                                                                              Hamposyl ® L                                                                           DMPABA      propoxyl                                                                           +  o  +                                      160                                                                              Hamposyl ® O                                                                           DMPABA      acetate                                                                            +  o  +                                      161                                                                              Hamposyl ® O                                                                           DMPABA      lactate                                                                            +  o  +                                      162                                                                              Hamposyl ® O                                                                           DMPABA      propoxyl                                                                           +  o  +                                      163                                                                              Maypon ® 4C                                                                            2-acetylbenzoate                                                                          propoxyl                                                                           +  o  +                                      164                                                                              Maypon ® 4C                                                                            Maypon ® 4C                                                                           propoxyl                                                                           +  +  +                                      165                                                                              Maypon ® 4C                                                                            PABA        propoxyl                                                                           +  o  +                                      166                                                                              N--dodecyltetrabromo-                                                                      N--dodecyltetrabromo-                                                                     propoxyl                                                                           o  o  o                                         phthalamate  phthalamate                                                   __________________________________________________________________________

The effect of chain length of the amido carboxyl moiety and modifiermoiety on film-forming, substantivity and hydrophobicity can be seenfrom these Examples. The wide variety of active moieties that can beincluded in organozirconium compounds of the present invention is alsoillustrated.

EXAMPLE 167

This Example illustrates the preparation of the organometalliccomposition (N-tetradecylsuccinamate)₁.25 (myristate)₁.25aluminum(hydroxide)₀.5.

The composition was prepared by adding 45 grams of a 20%N-tetradecylsuccinamic acid solution in mineral oil to 29.5 grams ofmineral oil in an open beaker, and heating the mixture to 93° C. Then,4.7 grams of aluminum isopopylate was added and the mixture was held at93° C. and stirred for 40 minutes. Myristic acid, 6.5 grams, was thenadded and the reaction mixture was stirred an additional 40 minutes at93° C. Water, 0.2 grams, was then added to the warm reaction mixture andthe mixture was allowed to cool to room temperature.

The organometallic composition so prepared may be used as an emollient.

Thus it can be seen that the present invention provides organometalliccompounds and compositions which can be adapted for use in many andvarious applications. The organometallic compounds and compositions ofthis invention are substantive with respect to many types of substratesand desirably form films when applied to a substrate. The latitudepermitted by the incorporation of an active moiety of choice allows thecompound to be tailored to specific applications. Additionally thehydrophobicity of these compounds may be suitably controlled as desired.

We claim:
 1. An organoaluminum compound having the general formula:##STR10## wherein R represents an amido carboxyl moiety selected fromthe group consising of: ##STR11## wherein R¹ and R² may be the same ordifferent and are selected from the group consisting of hydrogen, analkyl radical of from 1 to about 20 carbon atoms, an aryl or aralkylradical of from 6 to about 20 carbon atoms, and an alkenyl radical offrom 3 to about 20 carbon atoms; R³ is a hydrocarbyl radical of from 1to about 6 carbon atoms; and the sum of the carbon atoms in R¹ and R² isin the range of from 0 to about 40, and the sum of the carbon atoms inR¹, R² and R³ is at least 2;R" is a modifier moiety selected from thegroup consisting of hydroxyl, an alkoxy radical of from 1 to about 6carbon atoms, or a carboxyl radical of from 1 to about 6 carbon atoms;R', which may not be R or R", comprises an active moiety, said activemoiety being bonded to the aluminum by a linkage selected from the groupconsisting of carboxylate, sulfonate, phosphate, phosphite, oxa and thialinkages; said organoaluminum compound forming a substantive coatingwhen applied to a surface.
 2. An organoaluminum compound according toclaim 73 wherein R is selected from the group consisting of succinamate,N-akylsuccinamate wherein the alkyl has from 3 to about 18 carbon atoms,N,N dialkylsuccinamate wherein the alkyl has from 3 to about 18 carbonatoms, 6-acetamidohexanoate, N-acetylglycinate, N-alkylsarcosinatewherein the alkyl has from 1 to about 18 carbon atoms, coco hydrolysedanimal protein and N-dodecyltetrabromophthalamate;R' is selected fromthe group consisting of p-dimethylaminobenzoate, p-aminobenzoate,salicylate, 2-acetylbenzoate, benzoate, diethylphosphate, dodecanthiol,bishexadecylphosphate, pyruvate, octoxide, methylsulfate,acetylsalicylate, 2,2'-dihydroxyl-4,4"-dimethoxybenzophenone,2,4-dichlorophenoxyacetate, ascorbate, 4-methoxycinnamate, laurate,uraconate, monomethylphthalate, and myristate, and R" is selected fromthe group consisting of hydroxyl, acetate, lactate, n-propoxyl andisopropoxyl.